CN114539509B - Cross-linked conjugated polymer film and preparation method and application thereof - Google Patents
Cross-linked conjugated polymer film and preparation method and application thereof Download PDFInfo
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- CN114539509B CN114539509B CN202210212984.4A CN202210212984A CN114539509B CN 114539509 B CN114539509 B CN 114539509B CN 202210212984 A CN202210212984 A CN 202210212984A CN 114539509 B CN114539509 B CN 114539509B
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- polymer film
- conjugated polymer
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- crosslinked
- solution
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- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 28
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 59
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 25
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000001678 irradiating effect Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000001548 drop coating Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
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- 238000005507 spraying Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000007772 electrode material Substances 0.000 abstract description 42
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 52
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000010408 film Substances 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000012265 solid product Substances 0.000 description 9
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9h-carbazole Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 8
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
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- -1 polytetrafluoroethylene Polymers 0.000 description 8
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- 230000001351 cycling effect Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
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- 239000010409 thin film Substances 0.000 description 5
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 4
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
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- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
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- 239000011149 active material Substances 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000012650 click reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- H01G11/48—Conductive polymers
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a crosslinked conjugated polymer film, a preparation method and application thereof. The side chain of the cross-linked conjugated polymer film is modified with styrene groups and the multi-dendritic imidazole cross-linking agent is introduced, so that the cross-linking degree of the polymer can be improved, and a loose and porous surface structure is formed. The unique network structure is favorable for providing a larger contact area between the electrode material and the electrolyte so as to improve the ion transmission rate, and the cross-linked conjugated polymer film is used as a protective layer so as to improve the stability of the electrode material. The cross-linked conjugated polymer film has excellent electrochemical performance and cycle stability, and has good application prospect in the fields of electrochemical energy storage devices such as secondary batteries, supercapacitors and the like.
Description
Technical Field
The invention relates to a cross-linked conjugated polymer film capable of improving the cycling stability of an electrode material in an electrochemical energy storage device, and a preparation method and application of the cross-linked conjugated polymer film, and belongs to the technical field of organic storage materials.
Background
With the rapid growth of global economy, problems such as exhaustion of fossil fuel and environmental pollution are being aggravated, and there is an urgent need for efficient, clean and sustainable energy sources and new technologies related to energy conversion and storage. The development of electrochemical energy storage devices is now a critical feature of current energy applications.
The electrode materials in common secondary batteries such as lithium ions and potassium ions are severely expanded in volume due to the migration of lithium ions and potassium ions in the process of charging the battery, and the volume of the electrode materials is obviously reduced due to the migration of ions in the process of discharging. Such large and repeated volume changes can destroy the structure of the active material itself, and can also cause the active material to fall off from the current collector, severely affecting the cycling stability of the battery.
In the electrochemical circulation process of the super capacitor, the active substances attached to the surface of the current collector can change in morphology along with continuous penetration of electrolyte ions, so that the active substances are damaged and further fall off from the current collector, the capacitance is rapidly reduced, and the circulation stability is poor. This phenomenon is more serious on some smooth-surfaced current collectors such as ITO, FTO. These drawbacks limit the wide range of applications for supercapacitors. Therefore, how to improve the cycling stability of electrode materials in electrochemical energy storage devices has become a major issue
Disclosure of Invention
The invention aims to: in order to solve the problems of the prior art, a first object of the present invention is to provide a crosslinked conjugated polymer film that can improve the cycling stability of an electrode material in an electrochemical energy storage device, a second object of the present invention is to provide a method for preparing the crosslinked conjugated polymer film, and a third object of the present invention is to provide an application of the crosslinked conjugated polymer film in the preparation of a secondary battery or a supercapacitor.
The technical scheme is as follows: the main chain of the crosslinked conjugated polymer film is composed of carbazole and condensed ring conjugated groups, the side chain of the crosslinked conjugated polymer film modifies styrene groups and introduces a multi-dendritic imidazole crosslinking agent, and the surface of the crosslinked conjugated polymer film is of a loose porous structure.
The preparation method of the crosslinked conjugated polymer film comprises the following steps:
(1) Preparing carbazole monomers;
(2) Carbazole monomers react with condensed ring conjugated monomers to obtain chain polymers;
(3) Reacting the chain polymer with a styrene group to obtain a chain polymer with a side chain linked styrene group;
(4) Pre-crosslinking reaction is carried out on the chain polymer and the multi-dendritic imidazole crosslinking agent to obtain a pre-crosslinking solution;
(5) Modifying sulfhydryl on the surface of the electrode;
(6) And (3) dissolving the chain polymer with the side chain belt styrene groups in an organic solvent to prepare a solution, mixing the solution with a pre-crosslinking solution, covering the surface of the electrode with the surface modified sulfhydryl groups, irradiating with ultraviolet lamp, heating, and annealing to form an electrode protection layer film on the surface of the electrode, namely the crosslinked conjugated polymer film.
Further, in the step (1), the selected carbazole-based monomer has the following structure:
wherein R is an alkyl group of 1 to 12 carbon atoms, and X is a halogen atom.
Further, in the step (2), the chain polymer has the following structure:
wherein Ar represents a condensed ring conjugated unit; n is an integer between 20 and 300.
Further, ar is selected from one of the following units:
wherein R is H or alkyl or alkoxy containing 1 to 12 carbon atoms.
Further, in the step (3), the styrene group is provided for hydroxystyrene.
Further, in step (4), the multi-branched imidazole cross-linker comprises one of the following structures:
further, in the step (5), the material of the electrode is metal, metal oxide, silicon oxide, quartz plate, glass or polymer material; the sulfhydryl group modification on the electrode surface is to utilize o-mercaptobenzoic acid, p-mercaptobenzoic acid or a silane coupling agent with sulfhydryl group to carry out sulfhydryl functional modification on the electrode substrate.
Further, the o-mercaptobenzoic acid, p-mercaptobenzoic acid or silane coupling agent with mercapto group are respectively ultrasonically treated in ethanol, isopropanol and acetone for 15-20min before use; finally, the substrate of the electrode is subjected to mercapto functional modification by utilizing o-mercaptobenzoic acid, p-mercaptobenzoic acid or a silane coupling agent with mercapto groups and the like.
Further, in the step (6), the organic solvent is toluene or methanol, and the concentration of the solution prepared by the organic solvent is 8mg/mL.
Further, in the step (6), the organic solvent is toluene or methanol, and the coating adopts a spin coating, drop coating, spray coating or knife coating method.
Further, in the step (6), the irradiation with ultraviolet lamp is carried out in a 175V ultraviolet lamp box for 20-25min.
Further, in the step (6), the heating is performed in a vacuum oven at 100 ℃, 120 ℃, 140 ℃ and 160 ℃ for 1 hour respectively.
The invention also comprises application of the crosslinked conjugated polymer film in preparation of secondary batteries or supercapacitors.
The invention obtains a chain polymer through the reaction of carbazole monomers and condensed ring conjugated monomers, and the sulfur-alkene clicking reaction occurs between the crosslinkable styryl group introduced in the side chain of the chain polymer and the active electrode material grafted with mercapto so as to tightly connect the crosslinked polymer film and the substrate in a chemical bond mode. The cross-linked conjugated polymer film provided by the invention is firmly covered on the active material like a net, plays a good role in protecting the electrode material, and greatly improves the cycling stability of the material. The invention introduces a plurality of crosslinking agents to facilitate the formation of rough holes on the surface of the polymer film, and the unique structure is favorable for providing a larger contact area between the electrode material and the electrolyte so as to improve the ion transmission rate. In addition, it can buffer the volume change of electrode material in the charge-discharge process so as to raise the circulation stability of electrode.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the cross-linked conjugated polymer film provided by the invention greatly improves the cycling stability of the electrode, and the capacitance retention rate is in a continuous rising trend, and can still keep 140% of capacitance compared with the initial state after 30000 circles. The cross-linked conjugated polymer film provided by the invention can be widely applied to electrode materials such as metal, metal oxide, glass, silicon oxide, polymer and the like of various electrochemical energy storage devices.
Drawings
FIG. 1 is a CV diagram of a crosslinked conjugated polymer film electrode material of example 1 according to the present invention;
FIG. 2 is a graph showing the capacitance retention ratio of the cross-linked conjugated polymer thin film electrode material of example 1 according to the present invention;
FIG. 3 is a GCD diagram of the cross-linked conjugated polymer thin film electrode material of example 1 of the present invention;
FIG. 4 is a chart showing the microscopic morphology of the surface of the crosslinked conjugated polymer film electrode material of example 1 after 30000 cycles in the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
1. Preparation of carbazole monomers
1.0g of 2, 7-dibromocarbazole, 0.5g of NaH and 4.11g of 1, 8-dibromooctane were added to 7.5mL of DMF and reacted at 60℃for 24 hours to obtain a reaction solution. The reaction mixture was cooled to room temperature, 100mL of tap water was added, the mixture was extracted with 200mL of methylene chloride 3 times, the organic layer solutions were combined, washed with 200mL of saturated brine 3 times, and finally dried over anhydrous magnesium sulfate and filtered. Removing dichloromethane by a rotary evaporator to obtain a crude product, purifying the crude product by using a column chromatography (eluent is petroleum ether and dichloromethane are in a volume ratio of 12:1) to obtain a white solid product, and drying the white solid product in a vacuum drying oven to obtain carbazole monomers with the following structures:
2. synthesis of the Linear Polymer PCBDT75
The microwave reaction bottle is put into a magnet and nitrogen is introduced. After adding 51.6mg of carbazole monomer, 90.5mg of BDT75, 4mL of anhydrous toluene, and 0.4mL of anhydrous DMF into a microwave reaction flask, the air was purged with nitrogen. Rapid addition of 4mgPd 2 (dba) 3 、10mgP(o-tol) 3 And (3) introducing nitrogen to discharge air out of the sealed microwave reaction bottle, and carrying out microwave reaction for 3.5 hours at 50 ℃. The solution obtained after the reaction was poured into 100mL of methanol to precipitate a brick-red flocculent precipitate. And (5) carrying out suction filtration to obtain red solid powder. The linear polymer PCBDT75 is obtained by respectively carrying out rope extraction for 12.5 hours by using acetone at 82 ℃ and normal hexane at 92 ℃.
3. Linear polymer PCBDT75 side chain modified styryl group
0.075mmol of 4-hydroxystyrene and 0.625mmol of NaH were added to 2mL of anhydrous DMF and mixed to obtain a mixture. The mixture was stirred at room temperature for 4 hours to give a mixed solution, 0.0225mmol of the linear polymer PCBDT75 was dissolved in 4mL of anhydrous toluene, and then added to the mixed solution, and reacted at 40℃for 12.5 hours, and the solution was gradually clarified. The reaction mixture was then aspirated with a 20mL syringe, washed 3 times with 10mL of water, and then precipitated by dropping into 100mL of methanol. And filtering to obtain red solid powder, namely the linear polymer PCBDT75 of the side chain modified styrene group.
4. Preparation of the Pre-crosslinked solution
Into a 25mL single-necked flask were charged 20mg of PCBDT75 (0.02 mmoml) which was a linear polymer of a side chain-modified styrene group, 3.2mg of 1,3, 5-triisomidazole methylbenzene crosslinking agent (0.01 mmol), 0.4mL of anhydrous DMF and 4mL of anhydrous toluene, and the mixture was reacted at 100℃for 18 hours to obtain a pre-crosslinked solution having a concentration of 8mg/mL.
5. Preparation of electrode material and mercapto modification
FTO glass (9 x 50 mm) was sonicated sequentially with ethanol, isopropanol and acetone for 20min, then dried with nitrogen. 1g of ammonium paratungstate (NH) 4 ) 10 H 2 (W 2 O 7 ) 6 Dissolved in 95mL deionized water, and 3mL of concentrated hydrochloric acid was added dropwise while stirring. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and the clear solution became a pale yellow turbid liquid. Then adding 2mL of hydrogen peroxide, and stirring for 1h to form a uniform and stable transparent solution. The FTO glass was placed in a hydrothermal reaction kettle with the conductive surface facing down and forming an angle of 60 ° with the polytetrafluoroethylene liner. Slowly adding the transparent solution after the reaction into a polytetrafluoroethylene lining of a reaction kettle according to 80% of the total volume of the reaction kettle, reacting for 2 hours at 160 ℃, and naturally cooling to room temperature after the reaction is finished. Taking out the FTO glass with the substrate, washing with deionized water and ethanol in sequence, and air-drying. Then, the FTO with the substrate is soaked in an ethanol solution of o-mercaptobenzoic acid with the concentration of 10mM for modification for 36 hours, and the electrode material with modified mercapto is obtained.
6. Preparation of cross-linked conjugated polymer film electrode material
The linear polymer PCBDT75 of the side chain modified styrene group is dissolved in toluene as an organic solvent, mixed with a pre-crosslinking solution according to the mass concentration ratio of 1:1, 3mg of photoinitiator 2, 2-dimethoxy-phenylacetophenone and 6 mu L of catalyst dipropylamine are added to obtain a mixed solution, and the mixed solution is uniformly coated on a modified tungsten oxide electrode through a spin coater, wherein the spin speed of the spin coater is 1000rpm/s. Then transferring to 175V ultraviolet lamp box, irradiating for 20min, heating at 100deg.C, 120deg.C, 140deg.C and 160deg.C in vacuum oven for 1 hr, naturally cooling, washing with dichloromethane to remove excessive photoinitiator, and air drying to obtain the final product.
7. Electrochemical performance test of cross-linked conjugated polymer film electrode material
Adopts a three-electrode system, takes a platinum sheet electrode as a counter electrode and takes an Ag/AgCl electrode as a referenceThe electrode, the prepared cross-linked conjugated polymer film electrode material is a working electrode, the prepared electrolyte is 1mol/L sulfuric acid aqueous solution, and electrochemical test is carried out, and the results are shown in figures 1-3. FIG. 1 is a graph showing CV cycles and capacitance retention of a crosslinked conjugated polymer film electrode material of example 1 according to the present invention; as can be seen from FIG. 1, WO with a surface covered with a protective layer of crosslinked polymer 3 The effective cycle number of the composite electrode in the voltage range of-0.5 to 0.4V can reach 30000 circles, compared with WO under the same test condition 3 The electrode performance is improved by more than 50 times.
Fig. 2 is a graph showing the capacitance retention rate of the cross-linked conjugated polymer thin film electrode material of example 1 according to the present invention, wherein the increase rate of the previous 6000 turns is maximum, the increase rate of the 6000 th turn to 18000 th turn is reduced, the subsequent capacitance change fluctuates, and the capacitance retention rate can still reach 140% after 30000 turns. The cyclic test shows that the electrode material protected by the cross-linked conjugated polymer film has extremely strong cyclic stability.
FIG. 3 is a GCD graph of the cross-linked conjugated polymer thin film electrode material of example 1 according to the present invention; as can be seen from FIG. 3, when the current density is 0.1mA cm -2 When the area specific capacitance of the composite electrode was calculated to be 47.3mF cm -2 Compared with the single WO under the same test conditions 3 Specific area capacitance of electrode (29.29 mF cm) -2 ) The electrochemical performance of the electrode material protected by the cross-linked conjugated polymer film is improved.
8. Microcosmic appearance characterization of cross-linked conjugated polymer film electrode material
The microscopic surface morphology of the cross-linked conjugated polymer thin film electrode material was characterized by scanning electron microscopy, and the result is shown in fig. 4. Fig. 4 is a microscopic topography of the surface of the cross-linked conjugated polymer film electrode material before and after 30000 cycles, wherein a is a microscopic topography of the surface of the cross-linked conjugated polymer film electrode material before and b is a local enlarged view of the surface of the cross-linked conjugated polymer film electrode material after 30000 cycles. As can be seen from FIG. 4 a, the protective layer of the crosslinked conjugated polymer film in the initial state is shown in WO 3 The electrode surface is formed into a sheet containing various componentsA net of holes of a size to protect the WO at the bottom of the layer 3 The electrodes are firmly locked in the mesh. From fig. 4 b, it can be seen that the bottom of the protective layer originally exhibits a WO in the form of a rod-like or plate-like nanostructure 3 As the number of cycles increases, the direction of the spheroidization is gradually toward. Microsphere of WO 3 Is extruded from the pores of the protective layer, but does not fall off the entire electrode material, but is adhered to the polymer film, which may be associated with covalent bonds formed by the thiol-ene click reaction linking the bilayers. With the gradual increase and agglomeration of the microspheres, the microspheres WO of small particles 3 Is adhered to both sides of the protective layer of the crosslinked conjugated polymer film to agglomerate WO 3 It is firmly held by the pores between the cross-linked networks so that the whole electrode material remains a relatively stable whole.
Example 2
1. Preparation of carbazole monomers
1.0g of 2, 7-dibromocarbazole, 0.5g of NaH and 4.11g of 1, 8-dibromooctane were added to 7.5mL of DMF and reacted at 60℃for 24 hours to obtain a reaction solution. The reaction mixture was cooled to room temperature, 100ml of tap water was added, the mixture was extracted with 200ml of methylene chloride 3 times, the organic layer solutions were combined, washed with 200ml of saturated brine 3 times, and finally dried over anhydrous magnesium sulfate and filtered. Removing dichloromethane by a rotary evaporator to obtain a crude product, purifying the crude product by using a column chromatography (eluent is petroleum ether and dichloromethane are in a volume ratio of 12:1) to obtain a white solid product, and drying the white solid product in a vacuum drying oven to obtain carbazole monomers with the following structures:
2. synthesis of the Linear Polymer PCBDT26
Into a 25ml single-necked flask, 154.8mg carbazole monomer (0.3 mmol), 0.3mmol BDT26, 0.3mmol PIVOH, and 0.9mmol Cs were charged 2 CO 3 And 3mL of toluene, stirred and then bubbled with N 2 Oxygen removal and rapid addition of 3.36mg Pd (OAc) 2 、7.00mg P(O-OMePh) 3 Reflux is carried out for 8 hours at 100 ℃ to carry out polymerization reactionAfter the reaction, cooling to room temperature, pouring methanol into a single-mouth bottle, stirring with a magnet, repeating for three times, precipitating to obtain a product, standing, filtering, collecting precipitate, and extracting with acetone (82 ℃) and n-hexane (92 ℃) for 12.5h to obtain the linear polymer PCBDT26.
3. Side chain modified styrene group of straight-chain polymer PCBDT26
0.075mmol of 4-hydroxystyrene and 0.625mmol of NaH were added to 2mL of anhydrous DMF. After the mixture was stirred at room temperature for 4 hours, 0.0225mmol of the linear polymer PCBDT26 was dissolved in 4mL of anhydrous toluene and added to the above solution. The reaction was allowed to react at 40℃for 12.5h, the solution gradually becoming clear. The mixture was then aspirated with a 20mL syringe, washed 3 times with 10mL of water, and then precipitated by dropping into 100mL of methanol. And filtering to obtain red solid powder, namely the linear polymer PCBDT26 with side chain modified styrene groups.
4. Preparation of the Pre-crosslinked solution
Into a 25mL single-port flask were charged 20mg of a linear polymer PCBDT26 (0.02 mmoml) of a side chain-modified styrene group, 3.2mg of a 1,3, 5-triisomidazole methylbenzene crosslinking agent (0.01 mmol), and the solvent was anhydrous 0.4mL of DMF and 4mL of anhydrous toluene. The reaction was carried out at 100℃for 18h to give a pre-crosslinked solution at a concentration of 8mg/mL.
5. Preparation of electrode material and mercapto modification
FTO glass (9 x 50 mm) was sonicated sequentially with ethanol, isopropanol and acetone for 20min, then dried with nitrogen. 1g of ammonium paratungstate (NH) 4 ) 10 H 2 (W 2 O 7 ) 6 Dissolved in 95mL deionized water, and 3mL of concentrated hydrochloric acid was added dropwise while stirring. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and the clear solution became a pale yellow turbid liquid. Then adding 2mL of hydrogen peroxide, and stirring for 1h to form a uniform and stable transparent solution. The FTO glass was placed in a hydrothermal reaction kettle with the conductive surface facing down and forming an angle of 60 ° with the polytetrafluoroethylene liner. Slowly adding the solvent after the reaction into a polytetrafluoroethylene lining according to 80% of the total volume, reacting for 2 hours at 160 ℃, and naturally cooling to room temperature after the reaction is finished. Taking out the FTO substrate, washing with deionized water and ethanol in sequence, and air-drying. The substrate was then immersed in an ethanol solution of o-mercaptobenzoic acid at a concentration of 10mMAnd (3) modifying for 36h to obtain the sulfhydryl modified electrode material.
6. Preparation of cross-linked conjugated polymer film electrode material
The linear polymer with side chain modified styrene group is dissolved in toluene as organic solvent, mixed with pre-crosslinking solution in the mass concentration ratio of 1 to 1, 3mg of photoinitiator 2, 2-dimethoxy-phenyl acetophenone and 6 mu L of catalyst dipropylamine are added, and the mixed solution is uniformly coated on a modified tungsten oxide electrode through a spin coater with the spin speed of 1000rpm/s. Then transferring to 175V ultraviolet lamp box, irradiating for 25min, heating at 100deg.C, 120deg.C, 140deg.C and 160deg.C in vacuum oven for 1 hr, naturally cooling, washing with dichloromethane to remove excessive photoinitiator, and air drying to obtain the final product.
Example 3
1. Preparation of carbazole monomers
1.0g of 2, 7-dibromocarbazole, 0.5g of NaH and 4.11g of 1, 8-dibromooctane were added to 7.5mL of DMF and reacted at 60℃for 24 hours to obtain a reaction solution. The reaction solution was cooled to room temperature, 100ml of tap water was added, the mixture was extracted with 200ml of methylene chloride 3 times, the organic layer solutions were combined, washed with 200ml of saturated brine 3 times, and finally dried over anhydrous magnesium sulfate and filtered. Removing dichloromethane by a rotary evaporator to obtain a crude product, purifying the crude product by using a column chromatography (eluent is petroleum ether and dichloromethane are in a volume ratio of 12:1) to obtain a white solid product, and drying the white solid product in a vacuum drying oven to obtain carbazole monomers with the following structures:
2. synthesis of the Linear Polymer PCDTP46
Into a 25ml single-necked flask were charged 154.8mg of carbazole monomer (0.3 mmol), 0.3mmol of DTP46, 0.3mmol of PIVOH, and 0.9mmol of Cs 2 CO 3 And 3mL of toluene, stirred and then bubbled with N 2 Deoxidizing and adding 3.36mgPd (OAc) rapidly 2 、7.00mgP(O-OMePh) 3 After-vacuumizing towards N 2 Three times, return at 100 DEG CStream 8h was used for polymerization. Cooling to room temperature after the reaction is finished, pouring methanol into a single-mouth bottle, stirring with a magnet, repeating for three times, precipitating to obtain a product PCDTP46, standing, filtering, collecting precipitate, and extracting with acetone (82 ℃) and n-hexane (92 ℃) for 12.5 hours to obtain the linear polymer PCDTP46.
3. Side chain modified styryl group of straight-chain polymer PCDTP46
0.075mmol of 4-hydroxystyrene and 0.625mmol of NaH were added to 2mL of anhydrous DMF. After the mixture was stirred at room temperature for 4 hours, 0.0225mmol of the linear polymer PCDTP46 was dissolved in 4mL of anhydrous toluene and added to the above solution. The reaction was allowed to react at 40℃for 12.5h, the solution gradually becoming clear. The mixture was then aspirated with a 20mL syringe, washed 3 times with 10mL of water, and then precipitated by dropping into 100mL of methanol. And filtering to obtain red solid powder, namely the linear polymer PCDTP46 with side chain modified styrene groups.
4. Preparation of the Pre-crosslinked solution
Into a 25mL single-port flask were charged 20mg of a linear polymer of side chain-modified styrene group PCDTP46 (0.02 mmoml), 3.2mg of a 1,3, 5-triisomidazole methylbenzene crosslinking agent (0.01 mmol), a solvent of 0.4mL of anhydrous DMF and 4mL of anhydrous toluene. The reaction was carried out at 100℃for 18h to give a pre-crosslinked solution at a concentration of 8mg/mL.
5. Preparation of electrode material and mercapto modification
FTO glass (9 x 50 mm) was sonicated sequentially with ethanol, isopropanol and acetone for 20min, then dried with nitrogen. 1g of ammonium paratungstate (NH) 4 ) 10 H 2 (W 2 O 7 ) 6 Dissolved in 95mL deionized water, and 3mL of concentrated hydrochloric acid was added dropwise while stirring. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and the clear solution became a pale yellow turbid liquid. Then adding 2mL of hydrogen peroxide, and stirring for 1h to form a uniform and stable transparent solution. The FTO glass was placed in a hydrothermal reaction kettle with the conductive surface facing down and forming an angle of 60 ° with the polytetrafluoroethylene liner. Slowly adding the transparent solution after the reaction into a polytetrafluoroethylene lining of a reaction kettle according to 80% of the total volume of the reaction kettle, reacting for 2 hours at 160 ℃, and naturally cooling to room temperature after the reaction is finished. Taking out the FTO glass with the substrate, washing with deionized water and ethanol in sequence, and air-drying. However, the method is thatAnd then soaking the FTO with the substrate in an ethanol solution of o-mercaptobenzoic acid with the concentration of 10mM for modification for 36h, thus obtaining the electrode material with modified mercapto.
6. Preparation of cross-linked conjugated polymer film electrode material
The linear polymer with side chain modified styrene group is dissolved in toluene as organic solvent, mixed with pre-crosslinking solution in the mass concentration ratio of 1 to 1, 3mg of photoinitiator 2, 2-dimethoxy-phenyl acetophenone and 6 mu L of catalyst dipropylamine are added, and the mixed solution is uniformly coated on a modified tungsten oxide electrode through a spin coater with the spin speed of 1000rpm/s. Then transferring to 175V ultraviolet lamp box, irradiating for 20-25min, heating at 100deg.C, 120deg.C, 140deg.C and 160deg.C in vacuum oven for 1 hr, naturally cooling, washing with dichloromethane to remove excessive photoinitiator, and air drying to obtain the final product.
Example 4
1. Preparation of carbazole monomers
1.0g of 2, 7-dibromocarbazole, 0.5g of NaH and 4.11g of 1, 8-dibromooctane were added to 7.5mL of DMF and reacted at 60℃for 24 hours to obtain a reaction solution. After cooling the reaction solution to room temperature, 100mL of tap water was added, the mixture was extracted with 200mL of methylene chloride for 3 times, the organic layer solutions were combined, washed with 200mL of saturated brine for 3 times, and finally dried over anhydrous magnesium sulfate and filtered. Removing dichloromethane by a rotary evaporator to obtain a crude product, purifying the crude product by using a column chromatography (eluent is petroleum ether and dichloromethane are in a volume ratio of 12:1) to obtain a white solid product, and drying the white solid product in a vacuum drying oven to obtain carbazole monomers with the following structures:
2. synthesis of the Linear Polymer PCZ072
Into a 25mL two-necked flask, 0.1mmol of carbazole monomer, 0.1mmol of CZ072, 4mL of THF, and 2M concentration of K were charged 2 CO 3 1mL of aqueous solution, N is introduced 2 0.01mmol of tetrakis (triphenylphosphine) palladium was added rapidly and the solution was pale yellowRepeatedly introducing N 2 Three times. Reacting the reactants for 24 hours at 70 ℃, wherein the solution is dark reddish brown; and (3) dripping the reacted solution into 100mL of acetone, separating out white flocculent precipitate, and carrying out suction filtration to obtain a solid product. The resulting product was extracted with acetone (82 ℃) and n-hexane (92 ℃) each for 12h to give the linear polymer PCZ072.
3. Side chain modified styrene group of straight-chain polymer PCZ072
0.075mmol of 4-hydroxystyrene and 0.625mmol of NaH were added to 2mL of anhydrous DMF. After the mixture was stirred at room temperature for 4 hours, 0.0225mmol of the linear polymer PCZ072 was dissolved in 4mL of anhydrous toluene and added to the above solution. The reaction was allowed to react at 40℃for 12.5h, the solution gradually becoming clear. The mixture was then aspirated with a 20mL syringe, washed 3 times with 10mL of water, and then precipitated by dropping into 100mL of methanol. And filtering to obtain red solid powder, namely the linear polymer PCZ072 with side chain modified styrene groups.
4. Preparation of the Pre-crosslinked solution
Into a 25mL single-port flask were charged 20mg of a linear polymer PCZ072 (0.02 mmoml) of a side chain modified styrene group, 3.2mg of a 1,3, 5-triisomidazole methylbenzene crosslinking agent (0.01 mmol), a solvent of 0.4mL of anhydrous DMF and 4mL of anhydrous toluene. The reaction was carried out at 100℃for 18h to give a pre-crosslinked solution at a concentration of 8mg/mL.
5. Preparation of electrode material and mercapto modification
FTO glass (9 x 50 mm) was sonicated sequentially with ethanol, isopropanol and acetone for 20min, then dried with nitrogen. 1g of ammonium paratungstate (NH) 4 ) 10 H 2 (W 2 O 7 ) 6 Dissolved in 95ml deionized water, and 3ml of concentrated hydrochloric acid was added dropwise while stirring. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and the clear solution became a pale yellow turbid liquid. Then adding 2ml of hydrogen peroxide, and stirring for 1h to form uniform and stable transparent solution. The FTO glass was placed in a hydrothermal reaction kettle with the conductive surface facing down and forming an angle of 60 ° with the polytetrafluoroethylene liner. Slowly adding the solvent after the reaction into a polytetrafluoroethylene lining according to 80% of the total volume, reacting for 2 hours at 160 ℃, and naturally cooling to room temperature after the reaction is finished. Taking out the FTO substrate, washing with deionized water and ethanol in sequence, and air-drying. The substrate is then soaked at a concentration ofAnd (3) modifying the mixture in an ethanol solution of 10mM o-mercaptobenzoic acid for 36 hours to obtain the thiol-modified electrode material.
6. Preparation of cross-linked conjugated polymer film electrode material
The linear polymer with side chain modified styrene group is dissolved in toluene as organic solvent, mixed with pre-crosslinking solution in the mass concentration ratio of 1 to 1, 3mg of photoinitiator 2, 2-dimethoxy-phenyl acetophenone and 6 mu L of catalyst dipropylamine are added, and the mixed solution is uniformly coated on a modified tungsten oxide electrode through a spin coater with the spin speed of 1000rpm/s. Then transferring to 175V ultraviolet lamp box, irradiating for 20min, heating at 100deg.C, 120deg.C, 140deg.C and 160deg.C in vacuum oven for 1 hr, naturally cooling, washing with dichloromethane to remove excessive photoinitiator, and air drying to obtain the final product.
Through tests, the electrochemical performance and the cycling stability of the electrode are improved under the action of the cross-linked conjugated polymer film obtained in the examples 2-4, which shows that the cross-linked conjugated polymer film has good protection effect on the electrode.
Claims (9)
1. The crosslinked conjugated polymer film is characterized in that the main chain of the crosslinked conjugated polymer film is composed of carbazole and condensed ring conjugated groups, the side chain of the crosslinked conjugated polymer film modifies styrene groups and introduces a multi-dendritic imidazole crosslinking agent, the surface of the crosslinked conjugated polymer film is of a loose porous structure, and the multi-dendritic imidazole crosslinking agent comprises one of the following structures:
the preparation method of the crosslinked conjugated polymer film comprises the following steps:
(1) Preparing carbazole monomers;
(2) Carbazole monomers react with condensed ring conjugated monomers to obtain chain polymers;
(3) Reacting the chain polymer with a styrene group to obtain a chain polymer with a side chain linked styrene group;
(4) Pre-crosslinking reaction is carried out on the chain polymer and the multi-dendritic imidazole crosslinking agent to obtain a pre-crosslinking solution;
(5) Modifying sulfhydryl on the surface of the electrode;
(6) And (3) dissolving the chain polymer with the side chain belt styrene groups in an organic solvent to prepare a solution, mixing the solution with a pre-crosslinking solution, covering the surface of the electrode with the surface modified sulfhydryl groups, irradiating with ultraviolet lamp, heating, and annealing to form an electrode protection layer film on the surface of the electrode, namely the crosslinked conjugated polymer film.
2. The method for producing a crosslinked conjugated polymer film according to claim 1, comprising the steps of:
(1) Preparing carbazole monomers;
(2) Carbazole monomers react with condensed ring conjugated monomers to obtain chain polymers;
(3) Reacting the chain polymer with a styrene group to obtain a chain polymer with a side chain linked styrene group;
(4) Pre-crosslinking reaction is carried out on the chain polymer and the multi-dendritic imidazole crosslinking agent to obtain a pre-crosslinking solution;
(5) Modifying sulfhydryl on the surface of the electrode;
(6) And (3) dissolving the chain polymer with the side chain belt styrene groups in an organic solvent to prepare a solution, mixing the solution with a pre-crosslinking solution, covering the surface of the electrode with the surface modified sulfhydryl groups, irradiating with ultraviolet lamp, heating, and annealing to form an electrode protection layer film on the surface of the electrode, namely the crosslinked conjugated polymer film.
3. The method for producing a crosslinked conjugated polymer film according to claim 2, wherein in the step (1), the selected carbazole-based monomer has the following structure:
wherein R is an alkyl group of 1 to 12 carbon atoms, and X is a halogen atom.
4. The method of producing a crosslinked conjugated polymer film according to claim 2, wherein in the step (2), the chain polymer has the following structure:
wherein Ar represents a condensed ring conjugated unit, and n is an integer of 20-300.
5. The method for producing a crosslinked conjugated polymer film according to claim 4, wherein Ar is one selected from the group consisting of:
wherein R is H or alkyl or alkoxy containing 1 to 12 carbon atoms.
6. The method of producing a crosslinked conjugated polymer film according to claim 2, wherein in the step (3), the styrene group is provided as hydroxystyrene.
7. The method for producing a crosslinked conjugated polymer film according to claim 2, wherein in the step (5), the material of the electrode is a metal, a metal oxide, silicon oxide, a quartz plate, glass, or a polymer material; the sulfhydryl group modification on the electrode surface is to utilize o-mercaptobenzoic acid, p-mercaptobenzoic acid or a silane coupling agent with sulfhydryl group to carry out sulfhydryl functional modification on the electrode substrate.
8. The method for producing a crosslinked conjugated polymer film according to claim 2, wherein in the step (6), the organic solvent is toluene or methanol, and the coating is by spin coating, drop coating, spray coating or knife coating.
9. Use of the crosslinked conjugated polymer film according to claim 1 for the preparation of secondary batteries or supercapacitors.
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| CN104945602A (en) * | 2015-05-14 | 2015-09-30 | 华南理工大学 | Conjugated polymer material containing alkenyl/ alkynyl functional groups and click chemistry cross-linkable composition |
| CN105461903A (en) * | 2015-11-18 | 2016-04-06 | 华南理工大学 | Preparation of crosslinked electrode modification materials by adopting an olefinic bond-thiol group click chemistry method and applications of the materials in organic electronic devices |
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